Water-soluble azo dyestuffs



United States Patent ()filice 3,349,074 Patented Oct. 24, 1967 This invention relates to new azo compounds. More particularly the invention relates to Water-soluble metal complex azo compounds which contain reactive triazine or pyrimidine substituents, by means of which the compound can behave as a reactive dyestuff for textile materials containing acylatable amino and hydroxyl groups, such as natural andregenerated cellulose, wool, silk and polyamide fibrous materials, and are of particular value for the dyeing of leather.

Whilst it is known that the commercially-available reactive dyestuffs, developed primarily for the colouration of cellulose textile materials can be used for colouring leather, it is found in practice that the properties necessary to achieve good results on cellulose materials differ markedly in a number of respects from those advantageous for leather. One of the more important properties for a dyestulf for leather is its ability to penetrate the leather adequately but not too readily during dyeing. A dyestufi? which does not penetrate adequately and only colours a thin skin under the surface suffers from the disadvantage that the customary subsequent buffing treatments to the leather give rise to a variation in shade. On the other hand, a highly penetrative dyestuif gives weak shades and is relatively uneconomic in use.

It has now been found that certain reactive dyestuffs of the structure indicated hereinafter have properties most desirable for leather, having adequate but not too high a penetration, and affording principally strong brown shades but also other shades, having excellent fastness to washing, to rubbing and to light.

The compounds are water-soluble metal-complex azo compounds which contain copper, chromium or cobalt in complex union with an azo compound of the formula:

(CO)'OH111 R R1 R2 A-N=N-M-NT1-I IBI IT2 wherein M stands for a 1-hydroxy-3-sulpho-naphthalene radical connected to the azo group in the 2-position of the naphthalene nucleus and having the group attached to the 6- or 7-position of the naphthalene nucleus directly or through an anilino group,

n has the value 1 or 2,

A stands for a benzene or a naphthalene radical carrying the (CO)OH group in ortho position to the azo p.

R, R and R independently stand for hydrogen or for alkyl groups having up to 4 carbon atoms,

T stands for a linking triazine or a pyrimidine nucleus,

T stands for a dichlOro-s-triazine, trichloropyrimidine or a S-cyano-dichloropyrimidine radical,

B represents a monoazo radical of the formula wherein D is a benzene nucleus, which can optionally be substituted in ortho position to one of the nitrogen atoms by a chlorine atom or a nitro, sulphonic acid or carboxylic acid group, and E is the aromatic nucleus arising from a p-coupling primary or secondary amine of the benzene or naphthalene series or is a 5-pyr-azolone radical attached to the azo group at the 4-position of the pyrazole nucleus and carrying in the l-position of the pyrazole nucleus a monoor dicyclic radical of the benzene series to which the amino nitrogen atom is attached.

Broadly the new compounds can 'be considered to comprise an essentially brown, violet or tertiary shade metal complex dyestufl? linked by the radical T to a second azo moiety represented by B which is essentially yellow to orange in colour and which carries a reactive triazine or pyrimidine nucleus represented by T Where the metal in complex union with the compound of Formula 1 is copper, complexes having one atom of metal linked to one molecule of the compound are concerned; when the metal is cobalt or chromium, complexes having one atom of metal linked to two molecules of the compound are concerned.

The benzene and naphthalene radicals represented by A are derived from diazo components of the benzene and naphthalene series having a hydroxyl, alkoxy or carboxylic acid group ortho to the diazotisable amino group and can contain other substituents, such as chlorine atoms, or nitro, acetylamino or sulphonic acid groups.

The radical M can be represented, for example, by the formula:

r HOzS- NH 2 X L Y n11 where X stands for a hydrogen or a chlorine atom or for a sulphonic acid group, Y for a hydrogen atom or a sulphonic acid group and m for 1 or 2; or by the formula:

HOaS

where Y and m have the meanings just stated and Z stands for a hydrogen atom or a sul-phonic acid group.

As examples of alkyl groups which can be represented 'by R, R and R there are preferred n-alkyl radicals having 1 to 4, inclusive, carbon atoms, i.e. methyl, ethyl, pr-opyl and butyl.

The triazine or pyrimidine nucleus represented by T, is essentially a linking group and any substituent, attached thereto has little effect on the capability of acting as a dyestuif for leather. As examples of substituents which can be present on T there may be mentioned bromine or, preferably, chlorine atoms, sulphonic acid groups, thiocyano groups, negatively substituted aryloxy and aryl- O thio groups, such as sulphophenoxy, sulphophenylthio, nitrosulphophenoxy, disulphophcnoxy and sulphonaphthoxy; groups of the formula:

wherein R and R may be the same or ditferent and each represents a hydrogen atom or an alkyl, aryl or aralkyl group; also amino and hydroxyl groups, monoor disubstituted amino groups, etherified hydroxyl and etherified mercapto groups; in the case of substituted amino groups, this classincludes, for example, (a) monoand di-alkylamino groups in which the alkyl groups preferably contain at most 4 carbon atoms, and which may also contain such substituents as chlorine atoms or hydroxyl, alkoxy or sulphato groups and (b) phenylamino and naphthylamino groups preferably containing sulphonio acid substituents; in the case ofetherified hydroxyl and mercapto groups, this class includes, for example, alkoxy and alkylthio groups preferably those of low molecular weight, i.e. having up to about 4 carbon atoms and unsubstituted or positively substituted phenoxy phenylthio, naphthoxy or naphthylthio groups; as particular examples of all these classes there may be mentioned, for example, methylamino, ethylamino, dimethylamino, ,8- hydroxyethylarnino, di-(fl-hydroxyethyhamino, cyclohexylamino, anilino, sulphophenylamino, disulphophenylamino, carboxyphenylamino and sulphocarboxyphenylamino, methoxy, ethoxy and 'butoxy, phenoxy, methyl phenoxy, chlorophenoxy and phenylthio groups.

As examples of radicals represented by B there can be mentioned, for example,

1:4-phenylene nuclei of the formula:

1:4-naphthylene radicals of the formula:

where p stands for 1 or 2 and Y, for a hydrogen atom or a sulphonic acid group;

S-pyrazolone radicals of the formula:

in which I represents a methyl or carboxylic acid group and L stands for a benzene nucleus which may be substituted, for example by chlorine, methyl or sulphonic acid, or for a 2,2-disulpho-4,4"stilbene radical.

The water-soluble metal complex azo compounds of the invention can be obtained by re cting together cyanuric chloride, 5cyan0-2,4,6-pyrimidine or 2,4,5,6- tetrachloropyrimidine and a metal-complex aminoazo compound which contains copper, chromium or cobalt in complex union which an aminoazo compound of the formula:

(CO)OHi1-1 R R1 Ilia A-N=N-M-N-T11 IB-NH (10; wherein the symbls A, n, M, R, R R T and B have the meanings previously stated.

The above process can conveniently be carried out by stirring an aqueous suspension or solution of the cyanuric chloride or polyhalogenopyrimidine, adding an aqueoussolution of the compound of Formula 10 and simultaneously or on completion of the addition, adding a solution of an acid-binding agent. The function of the acid-binding agent is to neutralise the hydrogen halide as it is formed during the reaction. Accordingly any acid-binding agent may be used provided that it is not present in such quantity that it causes hydrolysis of the reactants or causes some other side-reaction. It is preferred to use an alkali metal carbonate or bicarbonate, added at such a rate that the pH of the mixture stays within the range of 6.0 to 8.0. The temperature of reaction may be between 0 C. and 100 C. dependent on the ease with which the reaction occurs. In general cyanuric chloride reacts Within a temperature range of 0 to 10 C, but polyhalogeno pyrimidines require a higher temperature of the order of 40 to C.

The compounds of Formula 10 can be obtained by .a combination of a condensation step and a diazotisation and coupling step. In the first step, preferably, a trihalogeno-1,3,5-triazine or a 2,4,6-trihalogenopyrimidine, is condensed with a water-soluble metal-complex containing copper, chromium or cobalt in complex union with an aminoazo compound of the formula:

(oo oH,.-r R

A-N=NMNH (11 wherein A, n, M and R have the meanings stated above.

The compounds of Formula 11 can themselves be obtained by diazotising a primary aromatic amine of the benzene or naphthalene series which contains the group in ortho position to the amino group and coupling the diazonium compound so obtained with a 1-hydroxy-3- sulphonaphthalene having a group of the formula NHR attached to the 6- or 7-position of the naphthalene nucleus directly or throughan anilino group.

As examples of primary aromatic amines of the benzene or naphthalene series which can be used, there may be mentioned, for example,

anthranilic acid,

S-nitroanthranilic acid, 5-sulphoanthranilic acid, 4-sulphoanthranilic acid, 4-ch1oroanthranilic acid, 4-nitro-2-amino phenol, 4-nitro-2-aminophenol-o-sulphonic acid, 6-nitro-2-aminopheno1-4-sulphonic acid,

S-nitro-Z-aminophenol, Z-aminoterephthalic acid, 5-nitro-2-aminoterephthalic acid, 6-nitro-1-amino-2-naphthol-4-sulphonic acid, 4-chloro-2-aminophenol-6-su-lphonic acid, 6-chloro-2-aminophenol-4-sulphonic acid, 2-aminophenol-4-sulphonic acid and 2-aminophenol-4:6-disulphonic acid.

As examples of 1-hydroxy-3-sulph0naphthalene compounds which can be used, there may be mentioned, for example,

The aminoazo compounds of Formula 11 can be converted to the required metal complex by customary methods, for example by heating the compound in a weakly acid, neutral or alkaline aqueous solution with a salt of the metal concerned, for example, chromium acetate, cobalt chloride or copper sulphate.

For introduction of the radical into the compound of Formula 10, the reaction product of the trihalogeno-1,3,5-triazine or trihalogenopyrimidine, or the primary condensation product of one of these, with the metal complex of the aminoazo compound of Formula 11, is first reacted with one of the following:

(a) A coupling component of the formula HE-NHR where E and R have the meanings stated above.

The new dyestuifs of the invention wherein B of Formula 1 stands for the radical of a monoazo dyestuff containing a 5-pyrazolone radical of the type stated above (for example, where the radical E has the structure set out under Formula 9 above) can also be obtained by coupling if, in the above processes just stated for manufacture of compounds of Formula 10:

In case (a) the product obtained by condensation with the coupling component H-E-NHR is coupled instead with a diazonium compound obtained from an aromatic amine of the formula 6 where D, R and T have the meaning stated above, and In case (b) the product obtained by condensation with the said compound is diazotised and coupled instead with a pyrazolone coupling component which carries in the 1- position of the pyrazole nucleus and a monoor di-cyclic radical of the benzene series to which a (where R and T have the meanings stated above) group is attached.

As examples of aromatic diamines which can be used in case (a) there may be mentioned, for example, 1,3- phenylene diamine-4-sulphonic acid, 1,4-phenylene diamine-3-sulphonic acid and 2-nitro-, 2-chloroand 2-carboxy-1,4-phenylene diamines.

As examples of diazotisable compounds which can be used in case (b), there may be mentioned, for example, those named in the last preceding paragraph, also 4-aminophenylsu-lphamic acid, 3-aminophenylsulphamic acid, 2-chloro- Laminophenylsulphamic acid, 2-methoxy-5-methyl-4-aminophenylsulphamic acid and 4-N-methylaminophenylsulphamic acid.

As examples of coupling components of the formula HENHR or HENHR there may be mentioned, for example, aniline, oand m-toluidines, 2,5-xylidine, oand m-anisidines, 2,5-dimethoxyaniline and 2-methoxy-5- methylaniline and the N-methyl and N-ethyl derivatives of these compounds also a-naphthylamine,

1-naphthy1amine-6- and 7-su-lphonic acids and Z-methoxy-1-naphthyla-mine-6- and 7-sulphonic acids,

1- 3 -aminophenyl) -3 -methyl-5-pyrazolone,

1-(4-aminophenyl) -3-methyl-5-pyrazolone,

1- (3 '-amino-4'-sulphohenyl) -3 -methy1-5-pyrazolone,

1- (4'-amino-3 -sulphophenyl) -3 -methyl-5-pyrazolone,

4-amino-4'-( 3 "-methylpyrazol-5"-on-1"-yl) stilbene- 2,2-disulphonic acid,

1- (3 -amino-2-methy1-5-sulphophenyl) -3 -methyl-5- pyrazolone, and

the corresponding compounds having a carboxylic acid group in place of the methyl group in the 3-position of the pyrazole nucleus.

Where it is desired that the triazine or pyrimidine nucleus represented by T in Formula 10 should contain a substituent other than a halogen atom, this substituent can conveniently be introduced after the condensation and diazotisation steps mentioned above.

Thus an amino or substituted amino group can be introduced by reaction with ammonia or a primary or second ary amine; an alkoxy or aryloxy (including negatively substituted aryloxy) group can be introduced by reaction with an alcohol, or aromatic hydroxyl compound; a sulphonic acid group can be introduced by reaction with an alkali metal sulphite; a thiocyano group can be introduced by reaction with potassium thiocyanate; a group of Formula 4 can be introduced by reaction with alkali metal salt of a mercaptoheterocyclic compound such as Z-mercaptobenzthiazole, Z-meroaptobenzselenazole, 2-mercaptobenziminazole, 2 mercaptobenzoxazole, 2 mercaptopyridine, 2- mercapto-6-methoxybenzthiazole, Z-mercapto 6 acetyl aminobenzthiazole, 2-mercapto-6 sulphobenzthiazole; a quaternary group can be introduced by treatment with pyridine or other tertiary amine; a group of Formula 5 above can be introduced by reaction with the appropriately substituted alkali dithiocarbamate such as sodium diethyldithiocarbamate, sodium dimetyldithiocarbamate, sodium diphenyldithiocarbamate and sodium pentamethylenedithiocarbamate; and a group of Formula 6 above can 7 be introduced by reaction with a thioamide such as thioacetamide and thioacetanilide.

The new water-soluble metal-complex azo compounds have high tinctorial strength and, in addition to their use for dyeing leather are valuable for colouring wool, silk, polyamide and more particularly natural and regenerated cellulose fibrousmaterials by the commonly-used methods applicable to reactive dyestuffs. For example, wool, silk and polyamide fibres can be dyed from an acid, neutral or weakly alkaline dyebath whereas cotton and other natural and regenerated cellulose materials may be dyed or printed with the new dyestuffs using an acid-binding agent to link the dyestuff directly to the fibre, for example as described and claimed in United Kingdom specifications Nos. 797,946, 798,121, 816,925, 819,585, 840,470, 822,047 and 838,336, or using a resin and acid catalystto act as an intermediate link, for example by the methods described and claimed in United Kingdom specifications Nos. 846,505 and 888,905.

The invention is illustrated but not limited by the following examples in which parts and percentages are by weight.

Example 1 A solution of 21 parts of the sodium salt of 1:4-phenylenediamine-3-sulphonic acid in 140 parts of water is added COzH O to a solution of 59.25 parts of the tri-sodium salt of the 1:2-chromium complex of 2-(4:6-dichloro-1:3':5'-triazin-2'-ylamino) 6 (2'-carboxyphenylazo)5-hydroxynaphthalene-7-sulphonic acid (which may be obtained as described in Example 1 of British patent specification No. 878,527) in 800 parts of water and the mixture is heated for 2 hours at 40 C., the pH being maintained at 7 by the gradual addition of a 10% aqueous solution of sodium carbonate. 170 parts of sodium chloride added and the precipitate is filtered off.

To a solution of 15.09 parts of the tetra-sodium salt of the bis-monochlorotriazinyl compound so obtained in 300 parts of water, there are added 11 parts of 2 N aqueous sodium nitrite solution and the mixture is added with stirring to a mixture of 7 parts of 36% aqueous hydrochloric acid solution, 50 parts ofwater and 50 parts of ice. The mixture is stirred at to C. for 15 minutes then the excess nitrous acid is removed by the addition of sulphamic acid.

2.3 parts of m-toluidine are dissolved in a mixture of 30 parts of water and 15 parts of 2 N aqueous hydrochloric acid solution and the mixture is stirred at 0 to 5 C. The suspension of the tetrazonium compound is added together with sufficient sodium acetate to maintain the mixture alkaline to Congo Red paper and the mixture is then stirred for 16 hours. The mixture is then filtered and the residue on the filter is washed with 30 parts of acetone.

A solution of 5.2 parts of the tetra sodium salt of the diaminotetrakisazo compound so obtained is parts of water is added to a stirred mixture of 2 parts of cyanuric chloride, 15 parts of acetone and 20 parts of water at 0 to 5 C., the pH being maintained at 7 by the addition of a 2 N aqueous solution of sodium carbonate. 4.7 parts of sodium diethylmethanilate and 0.3 part of sodium hydrogen sulphate are added, the dyestuif is precipitated by addition of 15 parts of sodium chloride and isolated by filtration. The filter cake is washed with 30 parts of acetone, then pasted with 0.94 part of sodium diethylmetanilate and 0.06 part of sodium hydrogen sulphate and dried.

The product soobtained is the 1:2-chromium complex of the compound of the formula:

It dyes leather in brown shades fast to light and wet treatments. Furthermore, when used to dye wooled sheep skins by an immersion method the dye yields brown shades having good reserve of the wool portion.

The following table summarizes further examples of the invention obtained by a process similar to that described in Example. 1. One molecular proportion of the halogenoheterocyclic compound listed in column 3 is condensed successively with one-half of one molecular proportion of the 1:2 chromium (or cobalt) complex of the aminomonoazo compound listed in column 2 and one molecular proportion of the diamine listed in column 4, one molecular proportion of the diaminodiazo compound so obtained is tetrazotized and coupled with two molecular proportions .of the coupling component listed in column Sand the diaminotetrakisazo compound so obtained is condensed with two molecular proportions of the halogenoheterocyclic compound listed in the sixth column of the table.

Ex. 2 3 4 5 6 Shade 2 Cyanuric chloride.-- 2-amino-6-(2-carboxyplieny1- 1,4phenylene l-naphthylamine-fi- Cyanuric chloride Brown.

azo)5-naphthoL7-sulphonic diamine-2- sulphonic acid. acid (Cr). sulphonic acid. 3 do o l-naphthylamine-7- do D sulphonic acid. 4 d do .do Z-methoxy-l-naphthylado Do.

mine-G-sulphonic acid. 5 d0 d N-methylaniline rin D a do do 4-amino4-(3"-methyldo D pyrazal-5"-on-1-yl) stilbene-2,2-disu]pl1onic acid. 7 do rln do m-Ur ido lina 5-c an .2,4,6 m 1 pyrimidine. s d0 .rl n 1 ,3-ph enylene 1-naph th y1aInine-7- Cyanuric chloride D0.

diamine-tsulphonic acid. sulphonic acid. 0 fln i do do l-naphthylamine-fido D sulphonic acid.

Ex 2 3 4 5 6 Shade 10- Cyanuric ch1oride 2-amino-6-(2-carboxyphenyl- 1,4-phcnylene 1-(3-amino-4-sulpho- Cyanuric acid. Brown.

azo)-5-uaphth01-7-sulphonic diatninc-zphe11y1)-3-methyl-5- acid (CL). sulphonic acid. pyrazolone.

11 do .d0 .d0 m-Toluidine do Do.

12 do 1-chl0ro-2-aruino-6-(2- d0 1-naphthylamine-7- 5-cyan0-2,4,6-trich1oro- Do.

carboxypheny1azo)-5- sulphonic acid. pyrimidine. 1(1gphth0l-7-sulphonic acid 13 do 2-amino-6-(2-hydroxy-3- 1,4-pheny1ene do do D sulpho5-nitropheny1azo)- diamine-3- 5-naphtho1-1,7- sulphonic acid. disulphonic acid (00).

14 do 0 ...do l-naphthylamine-G- do Do.

sulphonic acid.

15 do 2-amino-7-(2-hydroxy-3- do .do do Do.

sulpho-5-nitr0phenylaz0)- 8-6-sulphonic acid (G0).

16 do do do 1-naphthylamina7- do Do.

sulphonic acid.

17 d do 1,3-phenylene m-Toluidine 2,4,5,6-tetrachloropy- Do.

diamineirimidinc. sulphonic acid.

18 do 2-mcthy1amino-6-(2- lA-phenylcne 1-naphthy1amine-6- Cyanuric chloride D0.

carb0xyphenylaz0)-5- diamine-3- suiphonic acid. naphthol-7-sulphonic sulphonic acid. acid (Cr).

19 do do ..d0 1-naphthy1amine-7- do Do.

sulphonic acid.

20 do 2-amin0-6-(2-ca1'boxyphenyldo m-Toluidine do Orangeazo)-5-naphthol-7- brown. sulphonic acid (00).

21 do .do do l-naphthylamine-fido Khaki.

sulphonic acid.

22 do 2-amino-6(2-hydroxy-5- do .do do Bluishnitrophcnylazo)5-naphthol- OWn. 7-sulp1ionic acid.

23 do 2-amino-7-(2-hydroxy-3- do do do Greynitro-5-Sulphophenylazo) brown. 8-naphthol-6-sulphonio acid (00).

24 do Z-amino-fi-(2-hydroxy-3'- do do do Grey.

nitro-5-sulphophenylazo)-5- naphthol-l,7-disulph0nic acid (Or).

25 do 2-amino-7-(2-carboxypheny1- 1,3pheny1ene .do 2,4,5,6trichloro- Brown.

azo)-8-naphtho1-6- 'amineipyrimidine.

Sulphonic acid (00). sulphonic acid.

26 do 2-methy1amino-7-(2-hydroxy- .do m-Ureidoaniline Cyanuric chloride Eiaki.

5-sulphophenylaz0)-8- naphthol-G-sulphonic acid (Cr).

27 do 2-methylamino-7-(2-hydroxydo do .do Do.

5-sulphamylphenylaz0)8- naphthol-tisulphonic acid (Cr).

28 do 2-amino-6-(2-hydroxy-5- 1,4-phenylene l-naphthylamine-fido Brown.

nitr0-3-su1phophenylazo)- diamine-3- sulphonic acid. 5-naphtho1-7-sulphonic sulphonic acid. acid (Cr).

29 do 2-amino-6-(2-carboxy-4- do m-Aminoacetanilide do Do.

su1phopheny1azo)-5- naphthol-7-sulphonic acid (Or).

30 do 2-amino-6-(2'-carb0xy-4- do m-Ureidn nflin Do.

nitropheny1azo)-5- naphthol-1,7-disulphouic acid (00).

Example 31 Diazotised anthranilic acid is coupled with an equimolecular proportion of 2-(4' amino 3 sulphophenylamino)-5-naphthol-7-sulphonic acid, the aminomonoazo compound so obtained is coverted to the copper complex and the latter is condensed with an equimolecular proportion of cyanuric chloride as described in British patent specification No. 877,859.

To a solution of 41.5 parts of the disodium salt of the dichlorotriazine compound so obtained in 1700 parts of Water there is added a solution of 10.5 parts of the sodium salt of 1:4-phenylenediamine 3 sulphonic acid in 150 parts of Water and the mixture is stirred for 2 hours at 45 C., the pH of the mixture being maintained at 7 by the addition of a 10% aqueous solution of sodium carbonate. The mixture is treated with 10% w./v. of sodium chloride and the compound which is precipitated is filtered oif.

40.1 parts of the trisodium salt of the compound so diazonium suspension is added together with sufficient sodium carbonate to keep the mixture alkaline to Brilliant Yellow. The mixture is then stirred for 16 hours, 400 parts of sodium chloride are added and the precipitated aminodisazo compound is filtered off.

A neutral solution of 39.6 parts of the tetrasodium salt of the compound so obtained in 800 parts of water is added to a suspension of 555 parts of cyanuric chloride in a mixture of 70 parts of acetone, 200 parts of water 1':3:5-triazin-- 22. ylamino) 6 -(2"-carboxyphenyland 200 parts of ice, the temperature being maintained azo) naphthol 7 sulphonic acid in 800 parts of at 0-5 C. and the pH of the mixture being kept at WatenThe mixture is heated for 2 hours at 40 C. the 6.5-7 by the addition of a 10% aqueous solution of pH of the solution being maintained at 7 by the gradual sodium carbonate. The mixture is stirred for a further addition of 10% aqueous solution of sodium carbonate.

hour then 240 parts of sodium chloride are added and 110 parts of ammonium hydroxide liquor of s.g.=0.88 the mixture is filtered. are then added and the mixture is stirred at 90 C. for

Theresidue on the filter is mixed with 3.74 parts of 16 hours. The solution is cooled to C. and is then sodium diethylmetanilate and .26 part of sodium hydroacidified to Congo Red with concentrated hydrochloric gen sulphate and is then dried. 10 acid. The compound whichis precipitated is filtered off.

On analysis, the dyestuif composition is found to con- To a solution of 14.9 parts of the tertiary condensatain 2.9 atoms. of organically bound chlorine per moletion product from cyanuric chloride so obtained in 300 cule and is the 1:1 copper complex of the compound parts of water there are added 11 parts of a 2 N aqueous of the formula: solution of sodium nitrite and the resultant solution is 15 added with stirring to a mixture of 7 parts of 36% aqueous hydrochloric acid solution, 50 parts of water and SOKH OH COZH 50 parts of ice. The mixture is stirred at 05 C. for

N I I l 15 minutes, then the excess of nitrous acid is removed by o1-o \CNH the addition of sulphamic acid. 2.3 parts of m-toluidine l are dissolved in a mixture of 30'parts of water and 15 SQ3H parts of 2 N aqueous hydrochloric acid solution and the solution is stirred at 0-5 C. The suspension of NH N tetrazotised 'dyestutf is added to the amine solution to- 1 gether with sufficient sodium acetate to keep the mixture NH alkaline to Congo Red paper and the mixture is stirred l O N N for 16 hours. The mixture is then filtered and the residue :0 1 on the filter is washed with parts of: acetone. I 30311 A solution of 5.2 parts of the tetrasodium salt of the 0 diarnino-tetrakisazo compound so obtained in 150 parts 30 of Water is added with stirring to a mixture of 2 parts of cyanuric chloride, 15 parts of acetone and 20 parts of water at 0-5 C. The mixture is stirred for 2 hours at 05 C., the pH of the solution being maintained at 7 by the addition of a 10% aqueous solution of sodium carbonate. 4.7 parts of sodium diethyl-metanilate and It dyes cellulose fibres or leather in red-brown shades having good fastness to light and to washing.

Example 32 0.3 part of sodium hydrogen sulphate are added and the Following the procedure of Example 31, cyanuric chlodyesmfiis Precipitated y addition of 15 Parts Sodium ride is condensed with 1 mole of the copper complex chloride and isolated by filtration. The filtercake is f 2- 2' carboxy 4' sulphopheny1azo) 5. washed with 30 parts of acetone, then mixed with 0.94 naphth0l-7-sulph0r1ic a id and on mole of lA- h yl e part of sodium diethylmetanilate and 0.06 part of sodium diamine-3-sulphonic acid, the product is diazotised and hydrogen sulphate and dried. coupled with 1-naphthylamine-6-sulphonic acid and this The product so obtained is the 1:2-chromium complex product is condensed with one mole of cyanuric chloride. of the compound:

0 02H OH NHa C1 1 a t sour HO 3S NH-PJ (J-NH N=N C NHi J l-Cl The dyestutf so obtained dyes leather and cellulose It dyes cotton, viscose and leather in brown shades textile materials in pink shades. fast to light and wet treatments. Wooled sheepskins are Example 33 SZSSOEI'OWH shades having. good reserve of the wool Following theprocedufe OfEXamP1e cyanuric 61110 The following table summarises. further. examples of ride is Condens d th 6 H1016 0f the pp complex the invention obtained by a process similar to that deof 2 arnino-6-( Y Y' p p m' scribed in the above example- One molecular proportion s-naphthol-lJ-disulphonic acid and one 0f of the halogenoheterocyclic compound listed in column 2 Phenylene diamine'4'sulphonic acid, li'rodlmt 15 is condensed successively with one-half of one molecular diazotised and EP with ,l'naphthylamnle 7 proportion of the 1:2-chromium or cobalt complex of the phonic acid and this product is condensed with one mole aminomonoam compound listed in column 3, one molecw of cyanunc chlomde lar proportion of thediamine listed in column 4 and one h dyesuifl Obtained colours leather and cellulose molecular proportion of the compound listed in column texme materials m p urp 1e 5; the .diamino disazo compound is tetrazotised and cou- Example 34 pled with 2 molecular proportions of the coupling com: A solution of 21 parts f the sodium salt f 1;3 1- ponent listed in column 6 and the diarnino-tetrakisazo ene diamine-4-sulphonic acid in 140 parts of water i compound so obtained is condensed with two molecular added to a solutionof 59.25 parts of the trisodium salt proportions of the halogenoheterocyclic compound named of the 1:2-chromium complex of 2-(4':6-dichloroin column 7.

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Example .69

A solution of 13.05 parts of the sodium salt of 2- amino-5-naphthola7-sulphonic acid in 100 parts of water is added during minutes to a cooled suspension of 9.6 parts of cyanuric chloride in 60 parts of acetone, 100 parts of water and IOO parts of ice. The mixture is stirred for a further 30 minutes and neutralised to pH 6.5 by the addition of 10% aqueous sodium carbonate solution. 10.5 parts of the sodium salt of 1:4-phenylene diamine-2- sulphonic acid in 100 parts of water are then added and the mixture is stirred and heated at between and C. for 2 hours whilst the pH of the mixture is maintained at 7.0 by the addition of 10% aqueous carbonate solu tion. 27 parts of ammonia liquor of s.g. 0.89 are added and the mixture is stirred and heated at 80 C. for 16 hours and cooled to 10 C.

6.85 parts of anthranilic acid are diazotised in the usual manner and added to the solution. The mixture is stirred at between 5 and 10 C. and pH 7.5 for 6 hours. 120 parts of salt and 40 parts of 36% aqueous hydrochloric acid solution are added and the precipitate is filtered oft and dried.

29.32 parts of the trisodiurn salt of the am compound so obtained are dissolved in a mixture of 1,500 parts of water and 40 parts of glacial acetic acid. A solution of 75 parts of chromium acetate in 350 parts of water is then added and the mixture is heated at 95 C. for 18 hours. 185 parts of salt and 100 parts of 36% aqueous hydrochloric acid solution are added and the precipitate is filtered off, washed with 200 parts of 20% brine and dried.

27.4 parts of pentasodium salt of the 1:2 chromium complex so obtained are dissolved in 800 parts of water, 6.6 parts of a 40% solution of sodium nitrite are added and the mixture is added to a mixture of 20 parts of 36% aqueous hydrochloric acid solution and 50 parts of water. The mixture is stirred for 1 hour at 10 C. and the excess nitrous acid destroyed with sulphamic acid. A solution of 9.5 parts of the sodium salt of l-naphthylarnine- 6-sulphonic acid in 50 parts of water is added and the pH is adjusted to 5.5 by the addition of sodium acetate; The mixture is then stirred for 18 hours at 5-10 C., filtered and the product on the filter is dried.

29.73 parts of the heptasodium salt of the 1:2-chromium complex compound so obtained are dissolved in 400 parts of water and the solution is added to a cooled suspension of 6 parts of cyanuric chloride in 30 parts of acetone, parts of ice and 50 parts of water. The mix- 50 ture is stirred for 1 hours at, 0 to 5 C. whilst maintaining a pH of between 6.0 and 7.0 by the addition of a 10% aqueous solution of sodium carbonate. 3.2 parts of sodium diethylmetanilate, 0.2 part of sodium bisulphate and 106 parts of salt are then added and the precipitate is 5 filtered offaThe filtercake is slurn'ed with 300 parts of acetone, refiltered and the product so obtained is mixed with 1.6 parts of sodium diethylmetanilate and 0.1 part of sodium bisulphate and dried.

of the compound of the formula:

16 It dyes cellulose textile materials and leather in brown shades fast to washing and to light.

Example Following the procedure of. Example 1, the 1:2-chromium complex of 2-amino-6-(2-carboxyphenylazo)-5- naphthol-7-sulphonic acid is condensed with 2 moles of cyanuric chloride and the product is condensed with 2 moles of 4-arninopheny1sulphamic acid. The product is tetrazotised, coupled with 2 moles of m-toluidine and the A solution of 42 parts (4 molecular proportions) of the sodium salt of 1:3-phenylenediamine-4-sulphonic acid in 280 parts of water is added tov a solution of 59.25 parts of the trisodium salt of the 1:2-chromium complex of 2(4'16' dichloro 1':3':5'-triazin-2'-ylamino)-6-(2'-car boxyphenylazo)-5-naphthol-7-sulphonic acid in 800 parts of water and the mixture is heated for 2 hours at 40 C., the pH of the solution being maintained at 7 by the gradual addition ofa 10% aqueous solution of sodium car bonate. The mixture is then heated to C. and stirred for 16 hours, the pH of the mixture being maintained at 7-8 by the addition of a 10% solution of sodium carbonate. The mixture isallowed to cool then acidified to Congo Red with 36% aqueous hydrochloric acid solution and the precipitate is filtered off.

To a solution of, 1879 parts of the heptasodium salt of the compound so obtained in 270 parts ,of water there are added 20 parts of a 2 N aqueous solution of sodium nitrite and the resultant solution is added with stirring to a mixture of .15 parts of a 36% aqueous solution of hydrochloricacid, 50 parts of water and 50 parts of ice. The suspension is stirred at 0-5C. for 1 hour then the excess of nitrous acid is removed by the addition of sulphamic acid. The suspension is added to a solution of 9.8 parts of the sodium salt of 1-naphthylamine-6-sulphonic acid in parts of water at 05 C., together with sufficient sodium acetate to keep the mixture alkaline to Congo Red paper and the mixture is then stirred 1 for 16 hours. The mixture is then filtered and the residue on the filter is washed with 30 parts of 10% brine.

A solution of 29 parts of the undecasodium salt of the compound so obtained in 400 parts of water is added with stirring to a mixture of 7.4 parts of cyanuric chloride, 40

' parts of acetone and 200 parts of water at 05 C. The

mixture is stirred for 2 hours at 05 C., the pH being maintained at 7 by the addition of a 2 N aqueous solution of sodium carbonate. 3.7 parts of potassium dihydrogenphosphate and 2.1 parts of disodium hydrogen phosphate are added, the dyestulf is precipitated by addition of parts of sodium chloride and isolated by filtration. The

60 filtercake is washed with 30 parts of acetone then pasted The dyestuff so obtamed is the 1:2-chromium complex with 1.85 parts of potassium dihydrogen phosphate and 1.05 parts disodium hydrogen phosphate and dried.

1 7 l 8 The product so obtained is the 1:2-chromium com- To a solution of 42.2 parts of the disodium salt of the plex of the compound of the formula: resultant product, there is added a solution of 14.55 parts son-1 o1 J; SO H Join OH a IFII N N N 1 NH -N=N NH-O o1 m N-o N H038 -NHC\ /N I NH N=N NH(|3 ("l-Cl N N 80311 v 0 S0311 $1 It dyes cellulosic fibres or leather in brown shades fast of the sodium salt of 1 (4'-amino-3-sulphophenyl)-3- to light and wet treatments. methyl-S-pyrazolone in 200 parts of Water and the mix- By replacing the 9.8 parts of the sodium salt of lture is stirred for 2 hours at 40 C. keeping the pH at naphthylamine-6-sulphonic acid by 47 parts of m-tolui- 7 by adding sodium carbonate solution. The mixture is dine, there is again obtained a dyestulf having similar cooled to 5 C. and a suspension of diazotised 5-(2',4'- properties and shade. dichloro-s-triazinylamino)aniline-2-sulphonic acid (ob- By replacing the 42 parts of the sodium salt of 1:3- tained from 9.4 parts of 1,3-pheuylene diamine-4-sulphenylenedia-mine-4-sulphonic acid used in the above exphonic acid) in 400 parts of water is added. ample by 42 parts of the sodium salt of 1:4-phenylene- The mixture is stirred for 16 hours at 5l0 C. and diamine-3-sulphonic acid there is obtained a dyestulf pH 7, then 4 parts of sodium diethylmetanilate, 0.25 part having similar properties and shade. of sodium bisulphate and 230 parts of salt are added. The Exam le 72 precipitated dyestuff is filtered olT, Washed with acetone, p mixed with 2 parts of sodium diethylmetanilate and 0.125 Following the procedure of Example 34, cyanuric chlopart of sodium bisulphate and dried. ride is condensed with 1 mole each of the copper complex The product is the 1:1-copper complex of the comof 2-(4"-amino-3-sulphophenylamino) 6 (2-carboxypound of the formula:

COzH C| H (I31 NN- I so H I OH 3 \N =CN=N Hms- NH N-o\ NHN H N/ S0;H

0 l Cli]\ (|JO1 phenylazo)-5-naphthol-7-sulphonic acid, 1,4-phenylene It dyes cellulose textile materials and leather in red brown diamine-Z-sulphonic acid and ammonia, the product is shades. diazotised and coupled with l-(4'-amino-3'-sulphophen- I claim: yl)-3-methyl-5-pyrazolone and the resultant product is 1. The metal complexes selected from the class concondensed with 1 mole of cyanuric chloride. sisting of 1:1-copper, 1:2-chromium and l:2-cobalt com- The dyestuff obtained colours cellulose textile materials plexes of bisazo dyestuffs of the formula: and leather in brown shades. It is the 1:1 copper com- (C(DHOH R1 plex of the formula: I l I AN=N-M NHYNTiNB-N--Tz m-l. S0311 N HiNC]l fiJ-NH 80311 \C/ NH N=N CH i NE \N (ll p-oi N=NO=C 503E H SO H n Example 73 Cyanuric chloride is condensed with one mole of the wherefn 1;1 complex f 2s 4" 1 3" 1 A is a rad cal selected from the class consisting of phenylamino)-6-(2'-carboxyphenylazo) 5 naphthol-7- 01311611346116 and o-naphthylene radicals,

sulphonic acid. 75 n has one of the values 1 and 2,

19 20 l M is a l-hydroxy-3-sulphonaphthalene radical conthe benzene series to which the amino group is nected to the azo group in the 2 position of the attached. naphthalene nucleus and to the 3. The lz2-chromium complex of the dyestuff of the formula: f 5 (NHYLn-iN 2K nlN-o o-Nnsoln group in one of the 6- and 7-pos1t1ons of the naphthalene nucleus, Y is selected from the class consist- N=N ing of m-phenylene, p-phenylene, monosulpho-m- 10 C phenylene and monosulpho-p-phenylene, m hasone 7 OH (302E of the values 1 and 2, R, R and R are independently selected from the class consisting of hydrogen and alkyl radicals having from H N 0-0 1 to 4 inclusive, carbon atoms, 1; l; T is selected from the class consisting of s-triazine and pyrimidine radicals, l

T is selected from the class consisting of 2,4-dichloro- SOHH C1 6-s-triazinyl, 5-cyano2,4-dichloro 6 pyrimidyl, 5- cyano 4,6 dichloro-2-pyrimidyl, 2,4,5 trichloro-6- pyrimidyl and a4,5,6-trichloro-2-pyrimidyl, and B is the radical of a monoazo compound of the formula:

' D N :N-E where1nD selected from the class 4. The 1:2-chromium complex of the dyestufi of the consisting of phenylene, monosulphophenylene, monf l osulphophenylene, monochlorophenylene, mononitro phenylene and monocarboxyphenylene and E is N an aromatic nucleus consisting of the residue of a SOaH coupling component H-ENHR which coupling I ll component is selected from the class consisting of N=N para coupling primary and secondary amines of the C benzene and naphthalene series and 5-pyrazolones I OH COQH carrying in the, 1-position of the pyrazole nucleus an at most dicyclic radical of the benzene series to which the amino group is attached. NH Nil-0 2. The 1:2-chromium complex of any dyestuff of the i; formula: C

oolH OH 50m &

HO S- NH-T1-NHBNHT1 5. The 1:2-chromium complex of the dyestuff of the formula: wherein T is selected from the class consisting of s-triazine and N pyrimidine radicals, H2N C% \C .NH SO3H T is selected from the class consisting of 2,4-dichloro- I ll i 6-s-t riazinyl, S-cyano 2,4 dichloro-6-pyrimidyl, 5- N=N cyano-4,6-dichloro 2 pyrimidyl, 2,4,5-trichloro-6- C i on N pyrimidyl and 4,5,6-trichloro-2-pyrimidyl, and COZH B is the radical of a monoazo compound of the formula: -DN:NE wherein D is selected from the N class consisting of phenylene, monosulphophen- H NHC/ \O G1 ylene, monochlorophenylene, mononitrophenyl- 11: ene and monocarboxyphenylene and E is an aromatic nucleus consisting of the residue of a coupling component H+E-NHR which coupling SOBH C1 component is selected from the class consisting 50311 of para-coupling primary and secondary amines of the benzene and naphthalene series and 5- pyrazolones carrying in the 1-position of the 6. The 1:2-chnomium complex of the dyestutt of thepyrazole nucleus an at most dicyclic radical of formula:

002E OH 01 CH; ('31 0 N N N \\N N N N/ \N 11038 NEE- tNH SOBH NH-iil (ii-Cl 21 22 7. The 1:2-chromium complex of the dyestuff of the No :references cited. formula:

N CHARLES B. PARKER, Primary Examiner. SO3H 5 D. M. PAPUGA, Assistant Examiner.

K H N OH COQH N 10 NH- NH-0 fil N N fi N 5 

1. THE METAL COMPLEXES SELECTED FROMTHE CLASS CONSISTING OF 1:1-COPPER, 1:2-CHROMIUM AND 1:2-COBALT COMPLEXES OF BISAZO DYESTUFFS OF THE FORMULA: 